Chemistry, The Central Science, 10th edition

Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten

Chapter 19
Chemical
Thermodynamics
John D. Bookstaver
St. Charles Community College
St. Peters, MO
2006, Prentice Hall, Inc.
Modified by S.A. Green, 2006

Chemical
Thermodynamics

First Law of Thermodynamics

You will recall from Chapter 5 that
energy cannot be created nor
destroyed.
Therefore, the total energy of the
universe is a constant.
Energy can, however, be converted
from one form to another or transferred
from a system to the surroundings or
vice versa.
Chemical
Thermodynamics

Spontaneous Processes
Spontaneous processes
are those that can
proceed without any
outside intervention.
The gas in vessel B will
spontaneously effuse into
vessel A, but once the
gas is in both vessels, it
will not spontaneously
Chemical
Thermodynamics

Spontaneous Processes
Processes that are
spontaneous in one
direction are
nonspontaneous in
the reverse
direction.

Chemical
Thermodynamics

Spontaneous Processes
Processes that are spontaneous at one
temperature may be nonspontaneous at other
temperatures.
Above 0C it is spontaneous for ice to melt.
Below 0C the reverse process is spontaneous.

Chemical
Thermodynamics

Reversible Processes
In a reversible process
the system changes in
such a way that the
system and
surroundings can be
put back in their original
states by exactly
reversing the process.
Changes are
infinitesimally small in
a reversible process.
Chemical
Thermodynamics

Irreversible Processes

Irreversible processes cannot be undone by

exactly reversing the change to the system.
All Spontaneous processes are irreversible.
All Real processes are irreversible.
Chemical
Thermodynamics

Entropy
Entropy (S) is a term coined by Rudolph
Clausius in the 19th century.
Clausius was convinced of the
significance of the ratio of heat
delivered and the temperature at which
it is delivered, q
T
Chemical
Thermodynamics

Entropy
Entropy can be thought of as a measure
of the randomness of a system.
It is related to the various modes of
motion in molecules.

Chemical
Thermodynamics

Entropy
Like total energy, E, and enthalpy, H,
entropy is a state function.
Therefore,
S = Sfinal Sinitial

Chemical
Thermodynamics

Entropy
For a process occurring at constant
temperature (an isothermal process):

qrev = the heat that is transferred when the

process is carried out reversibly at a constant
temperature.
T = temperature in Kelvin.
Chemical
Thermodynamics

Second Law of Thermodynamics

The second law of thermodynamics:
The entropy of the universe does not
change for reversible processes
and
increases for spontaneous processes.
Reversible (ideal):
Irreversible (real, spontaneous):
Chemical
Thermodynamics

Second Law of Thermodynamics

You cant break even
Reversible (ideal):

Irreversible (real, spontaneous):

Chemical
Thermodynamics

Second Law of Thermodynamics

The entropy of the universe increases (real,
spontaneous processes).
But, entropy can decrease for individual systems.
Reversible (ideal):

Irreversible (real, spontaneous):

Chemical
Thermodynamics

Entropy on the Molecular Scale

Ludwig Boltzmann described the concept of
entropy on the molecular level.
Temperature is a measure of the average
kinetic energy of the molecules in a sample.

Chemical
Thermodynamics

Entropy on the Molecular Scale

Molecules exhibit several types of motion:
Translational: Movement of the entire molecule from
one place to another.
Vibrational: Periodic motion of atoms within a molecule.
Rotational: Rotation of the molecule on about an axis or
rotation about bonds.

Chemical
Thermodynamics

Entropy on the Molecular Scale

Boltzmann envisioned the motions of a sample of
molecules at a particular instant in time.
This would be akin to taking a snapshot of all the
molecules.

He referred to this sampling as a microstate of the

thermodynamic system.

Chemical
Thermodynamics

Entropy on the Molecular Scale

Each thermodynamic state has a specific number of
microstates, W, associated with it.
Entropy is
S = k lnW
where k is the Boltzmann constant, 1.38 1023 J/K.

Chemical
Thermodynamics

Entropy on the Molecular Scale

Implications:

more particles
-> more states
-> more entropy
higher T
-> more energy states -> more entropy
less structure (gas vs solid)
-> more states
-> more entropy

Chemical
Thermodynamics

Entropy on the Molecular Scale

The number of microstates and,
therefore, the entropy tends to increase
with increases in
Temperature.
Volume (gases).
The number of independently moving
molecules.

Chemical
Thermodynamics

Entropy and Physical States

Entropy increases with
the freedom of motion
of molecules.
Therefore,
S(g) > S(l) > S(s)

Chemical
Thermodynamics

Solutions
Dissolution of a solid:
Ions have more entropy
(more states)
But,
Some water molecules
have less entropy
(they are grouped
around ions).
Usually, there is an overall increase in S.
(The exception is very highly charged ions that
make a lot of water molecules align around them.)

Chemical
Thermodynamics

Entropy Changes
In general, entropy
increases when
Gases are formed from
liquids and solids.
Liquids or solutions are
formed from solids.
The number of gas
molecules increases.
The number of moles
increases.

Chemical
Thermodynamics

Third Law of Thermodynamics

The entropy of a pure crystalline
substance at absolute zero is 0.

Chemical
Thermodynamics

Third Law of Thermodynamics

The entropy of a pure crystalline
substance at absolute zero is 0.

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Standard Entropies
These are molar entropy
values of substances in
their standard states.
Standard entropies tend
to increase with
increasing molar mass.
Chemical
Thermodynamics

Standard Entropies
Larger and more complex molecules have
greater entropies.

Chemical
Thermodynamics

Entropy Changes
Entropy changes for a reaction can be
calculated the same way we used for H:

S for each component is found in a table.

Note for pure elements:
Chemical
Thermodynamics

Practical uses: surroundings & system

Entropy Changes in Surroundings
Heat that flows into or out of the system
also changes the entropy of the
surroundings.
For an isothermal process:

Chemical
Thermodynamics

Practical uses: surroundings & system

Entropy Changes in Surroundings
Heat that flows into or out of the system also changes
the entropy of the surroundings.
For an isothermal process:

At constant pressure, qsys is simply

H for the system.
Chemical
Thermodynamics

A phase change is isothermal

(no change in T).
For water:

Hfusion = 6 kJ/mol
Hvap = 41 kJ/mol

Entropysystem

Link S and H: Phase changes

If we do this reversibly: Ssurr = Ssys

Chemical
Thermodynamics

Practical uses: surroundings & system

Entropy Change in the Universe
The universe is composed of the system and
the surroundings.
Therefore,
Suniverse = Ssystem + Ssurroundings
For spontaneous processes
Suniverse > 0
Chemical
Thermodynamics

Practical uses: surroundings & system

= Gibbs Free Energy

Chemical
Thermodynamics

Practical uses: surroundings & system

= Gibbs Free Energy

Make this equation nicer:

Chemical
Thermodynamics

Practical uses: surroundings & system

Gibbs Free Energy
TSuniverse is defined as the Gibbs free
energy, G.
For spontaneous processes: Suniverse > 0
And therefore: G < 0
G is easier to determine than Suniverse.
So:
Chemical
Use G to decide if a process is spontaneous.
Thermodynamics

Gibbs Free Energy

1. If G is negative, the
forward reaction is
spontaneous.
2. If G is 0, the system
is at equilibrium.
3. If G is positive, the
reaction is spontaneous
in the reverse direction.
Chemical
Thermodynamics

Standard Free Energy Changes

Standard free energies of formation, Gf
are analogous to standard enthalpies of
formation, Hf.

G can be looked up in tables,

or
calculated from S and H.
Chemical
Thermodynamics

Free Energy Changes

Very key equation:

This equation shows how G changes with

temperature.
(We assume S & H are independent of T.)
Chemical
Thermodynamics

Free Energy and Temperature

There are two parts to the free energy
equation:
H the enthalpy term
TS the entropy term

The temperature dependence of free

energy comes from the entropy term.
Chemical
Thermodynamics

Free Energy and Temperature

By knowing the sign (+ or -) of S and H,

we can get the sign of G and determine if a
reaction is spontaneous.
Chemical
Thermodynamics

Free Energy and Equilibrium

Remember from above:
If G is 0, the system is at equilibrium.
So G must be related to the equilibrium
constant, K (chapter 15). The standard free
energy, G, is directly linked to Keq by:

Chemical
Thermodynamics

Free Energy and Equilibrium

Under non-standard conditions, we need to use
G instead of G.

Q is the reaction quotiant from chapter 15.

Note: at equilibrium: G = 0.
away from equil, sign of G tells which way rxn goes
Chemical
spontaneously.
Thermodynamics

Gibbs Free Energy

1. If G is negative, the
forward reaction is
spontaneous.
2. If G is 0, the system
is at equilibrium.
3. If G is positive, the
reaction is spontaneous
in the reverse direction.
Chemical
Thermodynamics